Oxidized asphalt product and method of making same



N v- 2, 1948- R. B. KILLINGSWORTH E ITAL 4 OXIDIZED ASPHALT PRODUCT AND METHOD OF MAKING SAME Filed Dec. 18, 1945 FROM 50v. BOTTOMS FROM MICROWAX FILTRATE I80 4o ASPHALTIC STOCK.

I20 I40 I60 480 200 220 249 260 280 300 320 340 PENETRATION AT 77 F SOFTENING POINT (a. AND B.).'F

414 an c: E, eskfilsmuls |NVENTOR ATTORNEY Patentecl Nov. 2, 1948 UNITED, STATES PATENT OFFICE OXIDIZED ASPHALT PRODUCT AND METHOD OF MAKING SAME Robert B. Killingsworth, Douglaston, Harry. T.

Van Horn, Kew Gardens, and Wallace E. Spelshouse, Roslyn Heights; N. Y., assignors to Socony-Vacuum Oil Company, Incorporated, a corporation of New York Application December 18, 1945, Serial No. 635,758

2 Claims. ((21. 196-74).

crude, either as an overhead distillate cylinder stock or a residual cylinder stock, contains microcrystalline waxes. These microcrystalline waxes, frequently appearing in the literature and in the trade under the terms amorphous waxes or pe trolatum waxes are similarly of a crystalline nature, but of .such extremely small crystal size as to have given rise to the belief for a good many years that they were not possessed of a crystalline structure. In further refining of the cylinder stock cut, be it an overhead stock or a residual stock, it is customary to separate microcrystalline wax from it by a process of chilling agglomeration, of wax, and physical separation of wax from oil and crude petrolatum. Crude petrolatum is a stock consisting predominantly of microcrystalline waxes associated with some oily material. In thefurther working up of this crude petrolatum, itjis customary to dilute the'material with a solvent and bya process of further chilling and precipitation, separate from its microcrystalline waxes usually of about 150 melting point and higher, leavingbehind an oily material which contains apparently soften microcrystalline wax materials, some of the original cylinder stock fraction and other oily materials apparently related in nature more closely to the microcrystalline wax materials than to the fluid oils from which the waxes were separated. This is indicated by the high viscosity index of the material, which usually is above 80. We are not aware that these oily materials separated from crude petrolatum have heretofore been utilized for the manufacture of blown asphaltsand havefound that by blowing very unusual type of asphaltic material which has a properties suggesting its use either alone or in admixture with waxes either of paraffinic or microcrystalline nature to form coatings, rust preventive compounds, potting compounds, wire rope lubricants and laminating materials. For example, if these asphaltic materials are mixed in equal herein disclosed. One of the curves shows the these materials with airpand oxidizing them to form asphaltic materials of the usual grades of 130-140 softening point and higher, that we have been able toproduce blown asphaltic materials of a highly unusual nature.

In working up these oily materials, we have 3 found it advisable tofirst subject them to a dis-' tillation to remove from them lower boiling hydrocarbons constituting from 25% to 50% of the entire oily material and then to subject the remainder to blowing tening point grade.

In this manner, we have been able to make a to give asphalt of desired sof-" percentages with a petrolatum product of -135 melting point, it is found that an entirely homogeneous mixture results with no evidence of phase separation. The remarkable temperature-susceptibility characteristics of these 'asphalts suggests many other uses as modifiers of conventional asphalts to meet specialized requirements.

An idea of the rather unusual characteristics of these asphalts may be gained from inspection of the drawing attached to this specification, wherein asphalts prepared as herein disclosed are com pared with conventional blown asphaltic mate rials from usual sources as to penetration vs. softening point. In .this drawing the two lower curves are blown asphalt products from the indicated sources, onebeing from a Mid-Continent crude and the other from a conventional asphaltic stock. The upper two curves are for products characteristics of an asphalt produced by distilling from the oily starting material 25% of its content as lower boiling materials andthe other I shows the properties of asphalt produced after topping from the oily material 50% of its lighter boiling constituents. Two things are noticeable. First, the penetrations are considerably higher for the materials here disclosed than for conventional materials of the same softening point. Second, the slope of the curve is considerably 1 greater for the materials here disclosed than for 1 the conventional materials. No explanation is known at this time for the anomalous shape of the 50% bottoms curve. l

Exemplary of these products are .theltwo f'ollowing materials. First are described the two blowing stocks utilized for their production. These blowing stocks were derived inaccordance withthe description hereinbefore given by first separating a crude oil by distillation into a microcrystalline wax fraction, and separating from that microcrystallinewax fraction a crude petrolatum by chilling and'filtra-tion in the presence of amixed solvent consisting of benzol and methyl ethyl ketone. Next the crude petrolatum was de-oiled under similar but somewhat changed conditions in the same equipment and in the presence of thesame solvents. The oily mate rial separated vfrom the crude petrolatum in deoiling: was treated by distillation to provide: first a stock comprising a 50% bottoms of the original oily material and second, a stock comprising a 75% bottoms of the original oily material, whichstockszhad the following properties:

TABLE I Bottoms 5.0% Bottoms Viscosity Index These two stocks are then oxidized by blowing with air to produce aspl'ialtsv of .a conventional Both tine 50% and 75% bottoms oxidized to substances which are uifi'dueflin n properties, when compared with normal asphalts. They are much softer than conventional asphalts of corresponding softening points, are much more soluble in petroleum naphtha, and have good tem- .pera-ture-susceptibi1ity. They are miscible with petrolatums and microcrystalline waxes to a considerablyflgreater extent than regular asphalts. These oxidized bottoms, even of as high a hardness as 288 softening point, when used in thin films as paper laminants are flexible at temperatures as low as F. By comparison, Table IV below, sets forth comparable penetrations for asphalts of similar hardness produced by blowing a Mid-Continent :crude fraction and by blowing a conventionalasphaltio (Taico)? crude fraotion.

TABLE IV Oxidized asphalts from Mid-Continent crude Grade 130-140 5.1. 160-180 S. P. 180-200 S. P. 215-225 S; Pi

s;1 R &B),F

Penetration: 77.

32 F./200'gr./60'se 115 F150 gr./5 sec Oxidized asphalts from asphaltic (Taloo). crude Grade .1 -140 S. P. 160-180 SLP. 180-200 S.- P; 220-3235 SDP. .300315 SrPf S. P. (R& B), F H 136% 170. 193 v 234i. 314":

Penetration: 7 77 FJIOO gr./5 sec 58 33 25 19 6 32'F./200 gr./60 sec 27 2O 18 151 8 5 115 F./50 gr./5 sec 173 63 48 8 Solubility:

. 88 Naphtha, per cent. 64.4 60.4.

0014, percent 99. 82 99.82 99.80 99 1162 CS2; per cent 99. 88 99. 85 99.85 99:75

range pi, softening points. Tine materials pro du'c ed from, the bottoms are shown. in;

Takingas a basis of comp-ariso'n the penetrae tions at 115? and 77 FQWenote thattheratiq of these two values is 3:1 fo'r the softer, grades of;

The materials produced by oxidizing 75% botton s 'are shownin Table 11 I.-.

TABnE III I Soft. Pen. Pen. Pen. g' fg Sol. 0011, (Rs 13) F 77 1go 5 32/200460 115 50 5 per can't per cent 11?, Too soft 99.80 99.91 204 163 215 75. 53 99. 82 258 95 122 98.13 284 72 91 61. 2o 1 9s. 13 329 56.19

on; soqoear' pue s'ifeqds'a; 1x1110 11 nnonnnnom. lowest ratios of 1 /2 1 only for the hardest jadesm while the novel asphalts herein disclosed maintain a ratio of 1%.:1 or less practically throughout therange shown.

Another approach for demonstrating the lesser change of consistency of the novel asphalts over a Wide range of temperatures consists in reviewing the relation between the softening point and penetration. From the nature of the ring and ball test it follows that at the temperature of the softening point all asphalts have a consistency of the same order of magnitude as measured by their resistance to sagging. As the temperature decreases, asphalts of equal temperature susceptibility should show the same penetration herein disclosed highly unique and highly usable articles of commerce.

We claim: 1

1. That method of making an asphalt of softening-point-penetration-temperature index of 00075 or less which comprises: subjecting a fraction by treating with a selective solvent for said oily fraction, and recovering the oily fraction from said separation, removing the lower boiling fractions of said oily material by distillasusceptibility and high penetration for a given high soft point, renders the asphaltic materials values at the same temperature level and astion, and blowing the distillation residue to prophalts with higher temperature susceptibility duce therefrom by oxidation an asphaltic mateshould show lower penetrations, or in other words 1 rial of at least 130-140 soft point grade. will become harder. Since the 188 soft point novel 2. That method of making an asphalt of sofasphalt has a penetration of 235 at 77 F. vs. a tening-point-penetration-temperature index of penetration of 29 for the 185 soft point Midfrom about 0.005 to about 0.006 which comprises: Continent grade and a penetration of for the subjecting a petroleum fraction containing a minearest 193 soft point asphalt from Talco crude, crocrystalline wax to separation of oil and wax. it must be concluded that the novel asphalt to produce therefrom a crude petr-olatum, sepahardens less as the temperature is lowered from rating the crude petr-olatum into microcrystalline about 185 to 77 F. The 304 soft point, 68 pen. 25 wax and an oily fraction by treating with a selecnovel asphalt may be compared similarly with tive solvent for said oily fraction, and recovering the 314 soft point, 6 pen. conventional asphalt. the oily fraction from said separation, removing The comparison remains also valid for the penethe lower boiling fractions of said oily material trations taken at 32 F. and 115 F. Pfeifier and by distillation, and blowing the distillation resi- Van Doormaals method of measuring the temdue to produce therefrom by oxidation an asperature susceptibility of asphalt in terms of phaltic material of at least 130-140 soft point. S. P. T. (softening-point-penetration-temperature index) is given in Abrahams Asphalts and ROBERT B. KILLINGSWORTI-I. Allied Substances, 5th edition, vol. 11, p. 1006 as HARRY T, VAN HORN. follows: 35 WALLACE E. SPELSHOUSE.

log 800-log pen. 77P F., 100 gr., 5 sec.

S. P. T.- S. P. (R & B) o F 77 REFERENCES CITED where 800 is the assumed penetration of all as- The following references are of reem'd in the phalts at the softening point temperature. The 40 file of this patent: lower the values of S. P. T., the lesser is the sus- UNITED STATES PATENTS ceptibility of asphalts to changes w1th temperature. Number Name Date The following tables give calculated S. P. T. 2,119,940 Carr et al June '7, 1938 values for the novel asphalts in comparison with 2,158,672 Carr et a1 May 16, 1939 those for conventional oxidized asphalts. 2,337,336 McCluer et al Dec. 21, 1943 NW1 i Tal Mid- Limagfi gigg g 1223 5? Asph lts Cont. Indiana s. P. (Ra B), 1 188 304 185 221 193 314 272 204 Pen. 77 100 5 235 as 29 21 25 c 15.5 14.5 s. P.T .0043 .0047 0133 .0110 .0130 .0090 .0088 .0080

From Abrahams 1. 0. table L11, Summary of Blown Asphalt.

Asphalts of the nature herein disclosed display an S. P. T. value of the order of .005 to .006, sel- CTHER REFERENCES dom over about .0075. Abraham: Asphalts and Allied Substances,

The unusual combination of good temperature- 4th ed., 1938, pages 833 and. 835 and table facing page 452. Pub. by Van Nostrand Co., Inc., New York, N. Y. 

